CN112452303B - Galla chinensis tannin/dendritic fiber type mesoporous silica nanoparticle composite material and application thereof in gallium recovery - Google Patents

Galla chinensis tannin/dendritic fiber type mesoporous silica nanoparticle composite material and application thereof in gallium recovery Download PDF

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CN112452303B
CN112452303B CN202011228498.9A CN202011228498A CN112452303B CN 112452303 B CN112452303 B CN 112452303B CN 202011228498 A CN202011228498 A CN 202011228498A CN 112452303 B CN112452303 B CN 112452303B
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dfns
composite material
mesoporous silica
gallium
tannin
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CN112452303A (en
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熊英
解丽莎
刘欣
单炜军
于海彪
王月娇
崔俊硕
娄振宁
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Liaoning University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material and application thereof in gallium recovery. The technical scheme adopted is as follows: the Chinese gall tannin/dendritic fibrous mesoporous silica microsphere composite material is prepared by taking Chinese gall tannin as a raw material, taking dendritic fibrous mesoporous silica microsphere as a matrix and glutaraldehyde as a cross-linking agent through a microemulsion system synthesis method. In weak acid solution, the maximum saturated adsorption quantity of gallium is 243.50 mg.g ‑1 And gallium ions can be selectively recovered from the six-membered ion mixed system, and the adsorption rate of the adsorbent to gallium can still reach more than 94% after ten adsorption analysis experiments. The preparation method provided by the invention is simple, the operability is strong, the prepared composite material has large specific surface area, more hydroxyl active sites exist, the adsorption quantity of elemental gallium is high, and the application value is wide.

Description

Galla chinensis tannin/dendritic fiber type mesoporous silica nanoparticle composite material and application thereof in gallium recovery
Technical Field
The invention belongs to the technical field of effective adsorption of gallium and nano composite material preparation, and in particular relates to a Chinese gall tannin/dendritic fiber-shaped mesoporous silica microsphere composite material which is formed by taking Chinese gall tannin as a raw material, dendritic fiber-shaped mesoporous silica microsphere as a matrix and glutaraldehyde as a cross-linking agent and aims at effectively adsorbing gallium from a solution containing metal ion gallium.
Background
Gallium is one of the important rare-earth elements, and has extremely low content (0.0015%) in the crust, but has very wide application. 90% of simple substance gallium is applied to the scientific and technological departments, and is mainly used for manufacturing LEDs, integrated circuits, microwave devices and the like. Gallium compounds are mainly used in the front-end fields of communication, optical fibers, electronics, automobiles, unmanned vehicles and the like. Among them, gallium arsenide is often used as the most promising semiconductor material for device fabrication and other fields. In addition, the melting point and the boiling point of gallium are greatly different, and the gallium can be used for preparing materials such as thermometers and the like. Therefore, the separation and extraction of gallium has attracted much attention.
The methods reported at present for enriching and recovering gallium from liquid phase are a lot and mainly comprise methods such as an ion exchange method, a displacement method, an extraction method, a precipitation method, an adsorption method and the like. Among them, the displacement method is limited in use because of the great consumption of gallium-containing compounds during the process; the precipitation method is to make gallium and precipitant produce precipitation reaction to form insoluble or slightly soluble compound, and the method is complex in operation and difficult to control; the extraction method utilizes the principle of similar compatibility to achieve the separation purpose, but has the defects of overlong extraction time, poor repeatability, high cost and the like; the electrolytic method is mainly used for extracting coarse gallium and refining gallium. The adsorption method has wide application range, can be recycled, has good selectivity to gallium, is environment-friendly, and is a common method for recycling gallium.
The gallnut tannin contains a large number of hydroxyl active sites and has the characteristics of strong adsorption capacity and environment-friendly materials. Lia team (Industrial)&Engineering Chemistry Research,2004,43,2222) the prepared adsorbent has a good adsorption capacity for Au (III) by immobilizing tannin on a collagen fiber substrate. At 303K, the maximum adsorption capacity of the adsorbent to gold ions can reach 877mg.g -1 . In addition, among the materials, a silicon dioxide material is selected as a matrix, but compared with the traditional mesoporous silicon dioxide material, the dendritic fiber-shaped mesoporous silicon dioxide nanoparticle (Dendritic Fibrous Nano-silica, DFNS) is spherical with a three-dimensional dendritic central radial pore canal and a multistage pore structure, and has the advantages of higher specific surface area, larger pore volume, higher pore permeability, better particle inner surface contact property and the like. In 2010, a dendritic mesoporous silica-based nanoparticle was prepared by the politewar team (angelw.chem.int.ed., 2010,49,9652) under a cyclohexane emulsion system. Subsequently, the Yang team (Journal of Hazardous Materials,2018,363,248) and the Roozbeh Soltani team (Chemosphere, 2020,239,124735) were successively modified by grafting DFNS to obtain adsorbents excellent in adsorption capacity. However, until now, there has been no report of adsorption of gallium by using an adsorbent prepared by compounding the above two materials.
Disclosure of Invention
In order to solve the technical problems, the invention prepares the gallnut tannin/dendritic fiber mesoporous silica composite material with high adsorption capacity.
The invention is realized by the following technical scheme: the preparation method of the Chinese gall tannin/dendritic fiber type mesoporous silica nanoparticle composite material comprises the following steps:
1) Adding Tetraethoxysilane (TEOS) into a mixed solution of cyclohexane and n-amyl alcohol to obtain a mixed solution A; uniformly mixing bromocetyl pyridine (CPB), urea and deionized water to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, stirring at room temperature for 20-40 min, transferring into a high-pressure reaction kettle, performing hydrothermal reaction, cooling the obtained product to room temperature, washing with deionized water and acetone, drying at 60 ℃, calcining in a muffle furnace, and grinding the obtained solid to obtain a dendritic fiber mesoporous silica material (DFNS);
2) Placing DFNS into a round bottom flask, adding a toluene solution into the flask, reacting under a nitrogen atmosphere, then dropwise adding 3-aminopropyl triethoxysilane (APTES) into a reaction system, and continuing to react for 6-7 h; centrifuging, filtering, washing the obtained solid product with isopropanol and toluene, and vacuum drying to obtain an intermediate product DFNS-APTES;
3) Dissolving gallnut tannin in deionized water, fully stirring and dissolving, adding DFNS-APTES into the solution, continuously stirring the solution for 2 to 2.5 hours, slowly dripping glutaraldehyde solution, reacting the solution for 18 to 24 hours at 25 ℃, washing the obtained product with deionized water to be neutral, and drying the product in vacuum at 50 ℃ to obtain the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material.
Further, the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material comprises the following components in a volume ratio of 1) cyclohexane, n-amyl alcohol=20:1; CPB, urea=1.6:1 by mass ratio.
Furthermore, in the step 1), the hydrothermal reaction condition is that the temperature is 120-150 ℃ and the reaction is 3.5-4.0 h.
Further, in the step 1) of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material, the calcination condition in the muffle furnace is that the temperature is 540-560 ℃, the calcination time is 5-6 h, and the temperature rising rate is 3 min/. Degree.C.
Furthermore, in the step 2), 80-100 mL of toluene solution is added into 1.0-1.5 g of DFNS, and the reaction condition under the nitrogen atmosphere is that the temperature is 70-85 ℃ and the reaction time is 1-1.5 h.
Further, the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material comprises the following components in percentage by mass (step 3), wherein the Chinese gall tannin is DFNS-APTES= (0.3-0.5): 1.
The invention provides an application of a Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material as an adsorbent in gallium recovery.
Further, the method comprises the following steps: taking a solution containing gallium ions, regulating the pH value of the solution to be 3, adding the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material, and carrying out vibration adsorption for 3-5 h at the vibration rate of 180-200 r.min -1 Filtering and drying.
Further, the method comprises an elution step, wherein eluent is added into the dried composite material adsorbed with gallium ions, and the composite material is oscillated for 22-24 hours, taken out and filtered.
Further, the eluent is at a concentration of 0.1 mol.L -1 ～0.3mol·L -1 Is a HCl of (C).
The composite material is prepared by a synthesis method of a microemulsion system, the obtained adsorbent uses glutaraldehyde as a cross-linking agent, and aminated dendritic fiber-shaped mesoporous silica nanoparticles (DFNS-APTES) are combined with gallnut tannins to prepare the gallnut tannins/dendritic fiber-shaped mesoporous silica nanoparticle composite material which has a special central radial pore structure.
The invention uses the method of compounding dendritic fiber mesoporous silica nano particles and gallnut tannins to improve the adsorption performance of gallium. The method not only utilizes the water solubility of the gallnut tannin, but also solves the instability of the gallnut tannin in the adsorption process. Meanwhile, the method fully utilizes the advantage of good stability of the silicon dioxide material and the characteristic that the silicon hydroxyl on the surface of the silicon dioxide material has better adsorption capacity, further improves the adsorption performance of the adsorption material on gallium, and solves the problems of few active sites, poor stability and poor adsorption selectivity of the adsorbent. In various silicon-based materials, dendritic fiber-shaped mesoporous silica nano-microspheres are selected as a matrix to be compounded with Chinese gall tannin, so that the Chinese gall tannin/dendritic fiber-shaped mesoporous silica composite material is prepared. In weak acid solution, the maximum saturated adsorption quantity of the adsorbent to gallium is 243.50 mg.g -1 And gallium ions can be selectively recovered from the six-membered ion mixed system, and the adsorption rate of the adsorbent to gallium can still reach more than 94% after ten adsorption analysis experiments. The method has simple operation and strong operability, and the adsorbent has large specific surface area, high adsorption performance on gallium element and high practical value.
The beneficial effects of the invention are as follows:
1. in the invention, the dendritic fiber mesoporous silica nanoparticle (DFNS) has unique structural characteristics of open nano pore canal, accessible inner space, large pore volume and the like, and gallium ions can be easily transported through a radial porous structure, so that effective load or reaction of the gallium ions and chemical active sites on the nano pore canal is realized.
2. In the invention, gallnut Shan Ningfu contains phenolic hydroxyl groups and has strong adsorption capacity to metals, but gallnut tannins have high water solubility, and tannins are fixed by compositing the gallnut tannins with dendritic fiber-shaped mesoporous silica nanoparticles, so that adsorption of tannins on gallium ions is realized, and the main mechanism is ion exchange action between Si-OH and Ga (III) on the surface of an adsorbent.
3. The Chinese gall tannin/dendritic fibrous mesoporous silica microsphere composite material prepared by the invention has larger specific surface area of 0.4-PT-10-DFNS, can be prepared by kilogram-level raw materials, and has simple preparation method and strong operability. The increase of the specific surface area leads to a significant increase of the adsorption quantity of gallium. The larger specific surface area makes more hydroxyl active sites existing on the surface of the composite material more concentrated, so that the stability is stronger.
4. The Chinese gall tannin/dendritic fibrous mesoporous silica microsphere composite material prepared by the invention has larger adsorption capacity to gallium in solution, and the maximum adsorption capacity reaches 243.50 mg.g -1 。
5. According to the invention, through experiments that the gallnut tannin/dendritic fibrous mesoporous silica microsphere composite material can selectively adsorb gallium ions from a six-element mixed system containing Ga (III), ge (III), al (III), ca (II), zn (II) and Cu (II), the practical application effect of the adsorbent is proved.
In conclusion, the gallnut tannin/dendritic fibrous mesoporous silica microsphere composite material prepared by the method can effectively adsorb gallium ions, is low in cost and easy to obtain raw materials, is simple in preparation method, can be prepared on a large scale, and has practical practicability.
Drawings
FIG. 1 is a schematic representation of the synthesis of the composite X-PT-Y-DFNS of the present invention.
FIG. 2 is a scanning electron microscope image of DFNS (A, B) and the inventive composite 0.4-PT-10-DFNS (C, D).
FIG. 3 is an infrared spectrum of DFNS, PT, and the composite of the present invention.
Fig. 4 shows the effect of different gallnut tannin additions on the adsorption performance of gallium at different acidity.
Figure 5 shows the effect of different gallnut tannins and glutaraldehyde additions on the adsorption performance of gallium at different acidity levels.
FIG. 6 shows adsorption isotherms of gallium (pH=3, t=48 h, T=303K) for DFNS (A), 0.3-PT-10-DFNS (B), 0.4-PT-10-DFNS (C), and 0.5-PT-10-DFNS (D).
FIG. 7 is a graph showing the selective adsorption of gallium in a mixed solution of 0.4-PT-10-DFNS of the composite material of the present invention.
Detailed Description
Example 1
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.4-PT-10-DFNS comprises the following steps:
1) Preparation of dendritic fibrous mesoporous silica material (DFNS): 2.5g of Tetraethylorthosilicate (TEOS) was added to a mixed solution consisting of 30mL of cyclohexane and 1.5mL of n-pentanol to obtain a mixed solution A. 1g of bromohexadecylpyridine (CPB), 0.6g of urea and 30mL of deionized water were uniformly mixed to obtain a mixed solution B. The mixed solution B is added into the mixed solution A dropwise, stirred at room temperature for 30min, poured into a 100mL high-pressure reaction kettle and subjected to hydrothermal reaction at 150 ℃ for 4h. After the obtained product is cooled to room temperature, deionized water and acetone are used for washing for 5 to 6 times in sequence. Then placed in a vacuum drying oven and dried at 60 ℃ for 12 hours. Calcining the obtained product in a muffle furnace for 6h (the temperature rising rate is 3 min/DEG C), and grinding the obtained solid product to obtain white powdery solid, namely the dendritic fiber mesoporous silica silicon material DFNS.
2) Preparation of DFNS-APTES: in a 150mL round bottom flask, 1.0g DFNS and 80mL toluene were added and reacted at 80℃under nitrogen for 1h. Then 1mL of 3-aminopropyl triethoxysilane (APTES) is added dropwise into the reaction system, the reaction is continued for 6h, the centrifugation and filtration are carried out, the obtained solid product is washed 5 times by isopropanol and toluene, and then the solid product is dried in vacuum at 60 ℃ to obtain an intermediate product DFNS-APTES.
3) Preparation of 0.4-PT-10-DFNS: dissolving 0.4g of Chinese gall tannin in 15mL of deionized water, fully stirring and dissolving, adding 1g of intermediate product DFNS-APTES into the mixture, continuously stirring the mixture for 2 hours, slowly dripping 10mL of glutaraldehyde solution with the concentration of 25% into the mixture, reacting the mixture for 24 hours at 25 ℃, washing the obtained product to be neutral by using deionized water, and drying the mixture at 50 ℃ in vacuum to obtain the Chinese gall tannin/dendritic fiber-shaped mesoporous silica nanoparticle composite material, wherein the Chinese gall tannin/dendritic fiber-shaped mesoporous silica nanoparticle composite material is named as 0.4-PT-10-DFNS (wherein 0.4 represents the gram number of the Chinese gall tannin added in the step 3), and 10 represents the addition amount of glutaraldehyde solution in the step 3). The synthetic route is shown in FIG. 1.
Example 2
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.4-PT-5-DFNS comprises the following steps:
the preparation was carried out as described in example 1, except that in step 3), 5mL of a glutaraldehyde solution having a concentration of 25% was used in place of 10mL of a glutaraldehyde solution having a concentration of 25% in example 1, and the resulting gallnut tannin/dendrimer-shaped mesoporous silica nanoparticle composite material was designated as 0.4-PT-5-DFNS.
Example 3
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.4-PT-15-DFNS comprises the following steps:
the preparation was carried out as described in example 1, except that in step 3), 15mL of a glutaraldehyde solution having a concentration of 25% was used in place of 10mL of a glutaraldehyde solution having a concentration of 25% in example 1, and the resulting gallnut tannin/dendrimer-shaped mesoporous silica nanoparticle composite material was designated as 0.4-PT-15-DFNS.
Example 4
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.3-PT-10-DFNS comprises the following steps:
1) Preparation of dendritic fibrous mesoporous silica material (DFNS): 2.5g of Tetraethylorthosilicate (TEOS) was added to a mixed solution consisting of 30mL of cyclohexane and 1.5mL of n-pentanol to obtain a mixed solution A. 1g of bromohexadecylpyridine (CPB), 0.6g of urea and 30mL of deionized water were uniformly mixed to obtain a mixed solution B. The mixed solution B is added into the mixed solution A dropwise, stirred at room temperature for 30min, poured into a 100mL high-pressure reaction kettle and subjected to hydrothermal reaction at 150 ℃ for 4h. After the obtained product is cooled to room temperature, deionized water and acetone are used for washing for 5 to 6 times in sequence. Then placed in a vacuum drying oven and dried at 60 ℃ for 12 hours. Calcining the obtained product in a muffle furnace for 6h (the temperature rising rate is 3 min/DEG C), and grinding the obtained solid product to obtain white powdery solid, namely the dendritic fiber mesoporous silica silicon material DFNS.
2) Preparation of DFNS-APTES: in a 150mL round bottom flask, 1.0g DFNS and 80mL toluene were added and reacted at 80℃under nitrogen for 1h. Then 1mL of 3-aminopropyl triethoxysilane (APTES) is added dropwise into the reaction system, the reaction is continued for 6h, the centrifugation and filtration are carried out, the obtained solid product is washed 5 times by isopropanol and toluene, and then the solid product is dried in vacuum at 60 ℃ to obtain an intermediate product DFNS-APTES.
3) Preparation of 0.3-PT-10-DFNS: dissolving 0.3g of Chinese gall tannin in 15mL of deionized water, fully stirring and dissolving, adding 1g of intermediate product DFNS-APTES, continuously stirring for 2h, slowly dripping 10mL of glutaraldehyde solution with the concentration of 25% into the mixture, reacting for 24h at 25 ℃, washing the obtained product with deionized water to be neutral, and vacuum drying at 50 ℃ to obtain the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material named as 0.3-PT-10-DFNS. The synthetic route is shown in FIG. 1.
Example 5
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.3-PT-5-DFNS comprises the following steps:
prepared as described in example 4 except that in step 3), 5mL of a 25% glutaraldehyde solution was used in place of 10mL of the 25% glutaraldehyde solution of example 1, and the resulting gallnut tannin/dendritic fiber shaped mesoporous silica nanoparticle composite material was designated as 0.3-PT-5-DFNS.
Example 6
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.3-PT-15-DFNS comprises the following steps:
the preparation was carried out as described in example 4, except that in step 3), 15mL of a glutaraldehyde solution having a concentration of 25% was used instead of 10mL of a glutaraldehyde solution having a concentration of 25% in example 1, and the resulting gallnut tannin/dendrimer-shaped mesoporous silica nanoparticle composite material was designated as 0.3-PT-15-DFNS.
Example 7
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.5-PT-10-DFNS comprises the following steps:
1) Preparation of dendritic fibrous mesoporous silica material (DFNS): 2.5g of Tetraethylorthosilicate (TEOS) was added to a mixed solution consisting of 30mL of cyclohexane and 1.5mL of n-pentanol to obtain a mixed solution A. 1g of bromohexadecylpyridine (CPB), 0.6g of urea and 30mL of deionized water were uniformly mixed to obtain a mixed solution B. The mixed solution B is added into the mixed solution A dropwise, stirred at room temperature for 30min, poured into a 100mL high-pressure reaction kettle and subjected to hydrothermal reaction at 150 ℃ for 4h. After the obtained product is cooled to room temperature, deionized water and acetone are used for washing for 5 to 6 times in sequence. Then placed in a vacuum drying oven and dried at 60 ℃ for 12 hours. Calcining the obtained product in a muffle furnace for 6h (the temperature rising rate is 3 min/DEG C), and grinding the obtained solid product to obtain white powdery solid, namely the dendritic fiber mesoporous silica silicon material DFNS.
2) Preparation of DFNS-APTES: in a 150mL round bottom flask, 1.0g DFNS and 80mL toluene were added and reacted at 80℃under nitrogen for 1h. Then 1mL of 3-aminopropyl triethoxysilane (APTES) is added dropwise into the reaction system, the reaction is continued for 6h, the centrifugation and filtration are carried out, the obtained solid product is washed 5 times by isopropanol and toluene, and then the solid product is dried in vacuum at 60 ℃ to obtain an intermediate product DFNS-APTES.
3) Preparation of 0.5-PT-10-DFNS: dissolving 0.5g of Chinese gall tannin in 15mL of deionized water, fully stirring and dissolving, adding 1g of intermediate product DFNS-APTES, continuously stirring for 2h, slowly dripping 10mL of glutaraldehyde solution with the concentration of 25% into the mixture, reacting for 24h at 25 ℃, washing the obtained product with deionized water to be neutral, and vacuum drying at 50 ℃ to obtain the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material named as 0.5-PT-10-DFNS. The synthetic route is shown in FIG. 1.
Example 8
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.5-PT-5-DFNS comprises the following steps:
prepared as described in example 7 except that in step 3), 5mL of a glutaraldehyde solution having a concentration of 25% was used in place of 10mL of the glutaraldehyde solution having a concentration of 25% in example 1, and the resulting gallnut tannin/dendritic fiber-shaped mesoporous silica nanoparticle composite material was designated as 0.5-PT-5-DFNS.
Example 9
The preparation method of the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material 0.5-PT-15-DFNS comprises the following steps:
the preparation was carried out as described in example 7, except that in step 3), 15mL of a glutaraldehyde solution having a concentration of 25% was used instead of 10mL of a glutaraldehyde solution having a concentration of 25% in example 1, and the resulting gallnut tannin/dendrimer-shaped mesoporous silica nanoparticle composite material was designated as 0.5-PT-15-DFNS.
Example 10 detection
FIG. 2 is a scanning electron microscope image of DFNS (A, B) and the inventive composite 0.4-PT-10-DFNS (C, D). As can be seen from the SEM morphology in fig. 2, the morphology of the functionalized dendritic fibrous mesoporous silica microsphere is not changed, but the outline of the functionalized dendritic fibrous mesoporous silica microsphere is blurred, and gallnut tannins are attached to the surface of the pore canal to cover part of the morphology of the DFNS. And is composed of N 2 The adsorption analysis structure shows that the adsorbent loaded with the gallnut tannin still belongs to mesoporous materials, and the specific surface area, the total pore volume and the pore diameter are reduced. Both can demonstrate that the gallnut tannins are successfully crosslinked on the dendritic fiber-shaped mesoporous silica microspheres.
FIG. 3 is an infrared spectrum of DFNS, PT, and the composite of the present invention. FTIR analysis also showed successful loading of gallnut tannins on dendritic fibrous mesoporous silica microspheres. The experimental results are also consistent with the scanning electron microscope images.
Example 11
Application of Chinese gall tannin/dendritic fiber type mesoporous silica nanoparticle composite material as adsorbent in recycling of scattered gallium
The adsorption effect of the composite material obtained by different gallnut tannin addition amounts on gallium under different acidity
The method comprises the following steps: the concentration of 10mLGa (III) was 20 mg.L -1 The pH value of the solution is regulated to be 1,2,3 and 10, the prepared composite material is respectively added, and the oscillation speed is 180-200 r.min at 30 DEG C -1 And (3) oscillating and adsorbing for 3-5 h, filtering and drying.
Fig. 4 shows the effect of different gallnut tannin additions on the adsorption performance of gallium at different acidity. As can be seen from fig. 4, as the pH increases, the adsorption rates of DFNS, DFNS-APTES, 0.3-PT-10-DFNS, 0.4-PT-10-DFNS, and 0.5-PT-10-DFNS all showed a tendency of increasing and decreasing in gallium, and the adsorption rate reached the maximum at ph=3, i.e., the optimal adsorption pH value at ph=3. The absorption rate of the adsorbent to gallium is obviously improved with the increase of the addition amount of the gallnut tannin when the pH=3, wherein the adsorption effect of the obtained adsorbent 0.4-PT-10-DFNS to Ga (III) is optimal when the gallnut tannin is added to be 0.4g, and the adsorption effect reaches 97%.
(II) adsorption effect of composite materials obtained by different gallnut tannins and glutaraldehyde addition amounts on gallium under different acidity
The method comprises the following steps: the concentration of 10mLGa (III) was 20 mg.L -1 The pH value of the solution is regulated to be 1,2,3 and 10, the prepared composite material is respectively added, and the oscillation speed is 180-200 r.min at 30 DEG C -1 Oscillating for adsorption for 3-5 hr, filtering and drying
Figure 5 shows the effect of different gallnut tannins and glutaraldehyde additions on the adsorption performance of gallium at different acidity levels. As can be seen from FIG. 5, the adsorption capacity of 0.4-PT-10-DFNS, which is an adsorbent synthesized by adding 10mL of glutaraldehyde crosslinking agent, was much higher than that of gallium ions, which is synthesized by adding 5mL or 15mL of glutaraldehyde, and the adsorption capacity of the adsorption material, which is synthesized with 0.4g of tannin as an initial amount, was the best. The adsorption capacity of the series adsorbents synthesized by the invention to gallium ions can reach more than 60 percent, and in addition, the adsorption capacities of the adsorbents 0.4-PT-10-DFNS, 0.3-PT-10-DFNS and 0.5-PT-10-DFNS to gallium ions are respectively 95 percent, 75 percent and 78 percent.
(III) adsorption isotherm of Ga (III) adsorption of the composite material synthesized by the invention
The method comprises the following steps: respectively weighing 10mg of adsorbent DFNS, 0.3-PT-10-DFNS, 0.4-PT-10-DFNS and 0.5-PT-10-DFNS, adding to 10mL of solution with pH=3, and concentrating to 20 mg.L -1 、50mg·L -1 、80mg·L -1 、100mg·L -1 、150mg·L -1 、200mg·L -1 In Ga (III) solution, and then the mixture is brought to a rotation speed of 180 r.min -1 In the shaking box of (2), shaking is carried out for 24 hours at 30 ℃. The results are shown in FIG. 6.
As can be seen from FIG. 6, the maximum saturated adsorption amounts of the adsorbents DFNS (FIG. 6A), 0.3-PT-10-DFNS (FIG. 6B), 0.4-PT-10-DFNS (FIG. 6C) and 0.5-PT-10-DFNS (FIG. 6D) to gallium were 70.08 mg.g, respectively -1 、187.16mg·g -1 、243.50mg·g -1 And 197.51 mg.g -1 . Obviously, 0.4-PT-10-DFNS has the best adsorption performance to gallium.
(IV) elution effect of different eluent on gallium-loaded adsorbent
The method comprises the following steps: 130mg of 0.4-PT-10-DFNS prepared in example 1 was weighed into a conical flask, and 100mL of 300 mg.L was added -1 Ga (III) solution with pH=3 at a rotation speed of 180 r.min -1 After 4 hours of oscillation in an oscillation box, filtering and drying. 10mg of the gallium-adsorbed adsorbent 0.4-PT-10-DFNS was weighed, 10mL of different eluents were added, and the mixture was shaken for 24 hours. The elution rates of the different eluents were calculated and the results are shown in table 1.
TABLE 1 elution effect of different eluents on gallium loaded with 0.4-PT-10-DFNS
As is clear from Table 1, the concentration was 0.1mol·L -1 The elution effect of HCl on 0.4-PT-10-DFNS adsorbing gallium is best and can reach 92.65 percent.
(V) adsorption selectivity of composite material as adsorbent to gallium
The method comprises the following steps: preparing a mixed ion solution containing six components of Ga (III), ge (III), al (III), ca (II), zn (II) and Cu (II), wherein the concentration of metal ions in the mixed ion solution is 20 mg.L -1 . Three 10mg portions of the adsorbent 0.4-PT-10-DFNS prepared in example 1 were added to the above mixed ion solutions of different pH (ph=1, 2, 3), shaken, filtered, and the concentration of each metal ion in the filtrate was measured.
As a result, as shown in FIG. 7, the adsorption capacity of 0.4-PT-10-DFNS to Ga (III) at pH=3 was 95% or more. The adsorbent 0.4-PT-10-DFNS has good selectivity under the condition of pH=3.
(six) cycle regeneration Performance of adsorbent
The method comprises the following steps: 150mg of 0.4-PT-10-DFNS was weighed and placed in 150mL, 50 mg.L -1 Shaking for 4 hours and filtering. Adding 0.5 mol.L of the dried adsorbent -1 Elution was performed with 130mL of HCl for 24h. Filtering, washing with water to neutrality, adding 120mL, 50mg.L -1 Shaking for 4 hours, filtering, washing with water, and performing 10 times of circulation. The gallium concentration in each filtrate and stock solution was measured and the results are shown in table 2.
TABLE 2 Cyclic regeneration experiments of 0.4-PT-10-DFNS
As can be seen from Table 2, after 10 adsorption-elution cycle experiments, the recovery rate of gallium is still as high as 94%, and 0.4-PT-10-DFNS has good cyclic regeneration capability.

Claims (10)

1. The preparation method of the Chinese gall tannin/dendritic fiber type mesoporous silica nanoparticle composite material is characterized by comprising the following steps of:
1) Adding tetraethyl orthosilicate TEOS into a mixed solution of cyclohexane and n-amyl alcohol to obtain a mixed solution A; uniformly mixing CPB, urea and deionized water to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, stirring at room temperature for 20-40 min, transferring into a high-pressure reaction kettle, performing hydrothermal reaction, cooling the obtained product to room temperature, washing with deionized water and acetone, drying at 60 ℃, placing into a muffle furnace for calcination, and grinding the obtained solid to obtain the dendritic fiber mesoporous silica material DFNS;
2) Placing DFNS into a round bottom flask, adding a toluene solution into the flask, reacting under a nitrogen atmosphere, then dropwise adding 3-aminopropyl triethoxysilane APTES into a reaction system, and continuing to react for 6-7 h; centrifuging, filtering, washing the obtained solid product with isopropanol and toluene, and vacuum drying to obtain an intermediate product DFNS-APTES;
3) Dissolving gallnut tannin in deionized water, fully stirring and dissolving, adding DFNS-APTES into the solution, continuously stirring the solution for 2 to 2.5 to h, slowly dripping glutaraldehyde solution, reacting the solution at 25 ℃ for 18 to 24 to h, washing the obtained product with deionized water to be neutral, and drying the product at 50 ℃ in vacuum to obtain the gallnut tannin/dendritic fiber mesoporous silica nanoparticle composite material.
2. The method according to claim 1, wherein in step 1), cyclohexane is n-pentanol=20:1 by volume; CPB, urea=1.6:1 by mass ratio.
3. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120 to 150 ℃ and a reaction temperature of 3.5 to 4.0. 4.0h.
4. The method according to claim 1, wherein the calcination in the muffle furnace is carried out at a temperature of 540-560 ℃ and a calcination rate of 5-6 h at a temperature rise rate of 3min/°c.
5. The process according to claim 1, wherein in step 2), 80 to 100. 100mL toluene solution is added to 1.0 to 1.5g of DFNS per 1.0 to 85℃under a nitrogen atmosphere, and the reaction is carried out at 1 to 1.5h.
6. The preparation method according to claim 1, wherein in step 3), gallnut tannins are prepared according to the mass ratio: DFNS-aptes= (0.3-0.5): 1.
7. Use of a gallnut tannin/dendritic fiber shaped mesoporous silica nanoparticle composite material prepared according to the method of any one of claims 1-6 as an adsorbent in the recovery of gallium.
8. The use according to claim 7, characterized in that the method is as follows: taking a solution containing gallium ions, regulating the pH value of the solution to be 3, adding the Chinese gall tannin/dendritic fiber mesoporous silica nanoparticle composite material, and carrying out vibration adsorption on the mixture for 3 to 5h with the vibration rate of 180 to 200 r.min -1 Filtering and drying.
9. The use according to claim 8, comprising an elution step, adding an eluent to the dried gallium ion-adsorbed composite material, shaking 22-24 h, taking out, and filtering.
10. The use according to claim 9, wherein the eluent is at a concentration of 0.1 mol-L -1 ～0.3 mol·L -1 Is a HCl of (C).
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